US4676969A - Method of synthesis of inorganic chalcogenides - Google Patents

Method of synthesis of inorganic chalcogenides Download PDF

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Publication number
US4676969A
US4676969A US06/877,084 US87708486A US4676969A US 4676969 A US4676969 A US 4676969A US 87708486 A US87708486 A US 87708486A US 4676969 A US4676969 A US 4676969A
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Prior art keywords
metal
container
tube
chalcogen
chalcogenides
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Expired - Fee Related
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US06/877,084
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Frank T. J. Smith
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Eastman Kodak Co
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Eastman Kodak Co
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Assigned to EASTMAN KODAK COMPANY, A CORP. OF NJ reassignment EASTMAN KODAK COMPANY, A CORP. OF NJ ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: SMITH, FRANK T.
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J15/00—Chemical processes in general for reacting gaseous media with non-particulate solids, e.g. sheet material; Apparatus specially adapted therefor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/20—Methods for preparing sulfides or polysulfides, in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/007—Tellurides or selenides of metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G11/00—Compounds of cadmium
    • C01G11/02—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/12—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G5/00—Compounds of silver
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/08—Sulfides

Definitions

  • the present invention relates to a method for preparing metal chalcogenides.
  • a common method of manufacturing metal chalcogenides is to precipitate them from aqueous solutions. This is accomplished by reacting a metal salt in solution with hydrides of chalcogens. For example, H 2 S (gas) is passed through a solution of cadium nitrate to form cadium sulfide (CdS). In this method undesirable metal oxides (CdO) are formed.
  • the object of this invention is to provide an improved method for producing finely divided metal chalcogenides which is not contaminated by undesirable metal oxides.
  • the drawing shows an apparatus which can be used to make chalcogenides in accordance with the invention.
  • the apparatus 10 includes a container in the form of a tube 12 which can be made of fused quartz or other heat resistant material.
  • the tube 12 is sealed at one end and is adapted to be placed within a furnace 14 such as a conventional resistance furnace. When placed in the furnace, the upper end of the tube 12 projects above the furnace 14 far enough so as to be unheated.
  • a header member 16 is secured by o-ring seals 18 to the top open end of the tube 12.
  • a source of inert argon gas 20 flows through a valve 22 to the interior of the header 16 and the tube 12 when the valve 22 is opened.
  • the tube and the header are vented through a valve 24.
  • the valve 24 is connected to a manostat 26 which can be adjusted to set the pressure inside the interior of the header 16 and the tube 12.
  • a middle chalcogen in accordance with this invention comprises the elements sulfur, selenium and tellurium. It is to be noted that oxygen and polonium which often are classified as chalcogens are not considered within the group of elements of middle chalcogens.
  • a solid phase elemental middle chalcogen is placed in the bottom of tube 12 which is then lowered into the furnace 14 and heated such that this material vaporizes completely.
  • the vaporized chalcogen then condenses as a liquid on the wall of the tube 12 close to its upper closed end.
  • the condensed liquid runs down the side of the tube into the furnace, boiling again when it reaches the temperature which its vapor pressure is equal to the ambient pressure, i.e., that pressure established by the manostat 26.
  • the inert argon gas is displaced out through the manostat until finally a vaporized chalcogen is established in the interior of the tube 12 at a controlled pressure.
  • the header 16 is provided with a horizontal portion 30 which receives metal pellets.
  • a pusher mechanism 32 when moved horizontally causes these metal pellets to drop down the center line of the header 16 into the tube 12 without touching the walls of the header or the tube. It should be noted at this point that pellets of metal alloys are also useful if mixed compounds of chalcogenides are desired.
  • the metal pellets react with the vaporized chalcogen. Once started, the reaction continues spontaneously during free fall of the pellets as the result of the rapid release of heat of reaction.
  • the tube 12 is selected to be long enough so that the reaction is completed before the metal pellets reach the lower end of the tube.
  • metal chalcogenides are produced in the form of a fine powder which deposits on the wall of the tube.
  • the rate of reaction is controlled by controlling the pressure, the rate of addition of metal, and the temperature of the furnace 14. Elemental sulfur, selenium and tellurium can be obtained commercially in extremely pure states. Moreover, argon which is extremely pure is also commercially available. Further, the high temperature reaction occurs away from the walls of the tube 12 during free fall. As a consequence of the above, the resulting chalcogenides are not contaminated with metal oxides.
  • the temperature of the furnace 14 was maintained at 1150° C. and the pressure at one atmosphere. Copper pellets of 1 mm diameter were dropped into the sulfur vapor and burned rapidly to produce copper sulfide (CuS).
  • CuS copper sulfide
  • a furnace temperature of 1100° C. and atmospheric pressure were found effective. By using a tube 12 of 5 cm diameter and 1 meter in length, approximately 2 moles of these compounds were prepared in single batches. The compounds were not contaminated with metal oxides.

Abstract

A method for forming metal chalcogenides is disclosed. An atmosphere of an elemental middle chalcogen is formed and a metal is reacted with the chalcogen in the vapor phase to form a metal chalcogenide powder.

Description

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method for preparing metal chalcogenides.
2. Description Relative to the Prior Art
A common method of manufacturing metal chalcogenides is to precipitate them from aqueous solutions. This is accomplished by reacting a metal salt in solution with hydrides of chalcogens. For example, H2 S (gas) is passed through a solution of cadium nitrate to form cadium sulfide (CdS). In this method undesirable metal oxides (CdO) are formed.
SUMMARY OF THE INVENTION
The object of this invention is to provide an improved method for producing finely divided metal chalcogenides which is not contaminated by undesirable metal oxides.
This object is achieved by a method for preparing metal chalcogenides which comprises the steps of:
(a) vaporizing a solid phase middle chalcogen into an inert atmosphere; and
(b) reacting a metal with such vaporized chalcogen in the vapor phase to form a finely divided metal chalcogenide.
BRIEF DESCRIPTION OF THE DRAWING
The drawing shows an apparatus which can be used to make chalcogenides in accordance with the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Turning now to the drawing where there is shown an apparatus 10 which can be used to practice the method in accordance with the invention. The apparatus 10 includes a container in the form of a tube 12 which can be made of fused quartz or other heat resistant material. The tube 12 is sealed at one end and is adapted to be placed within a furnace 14 such as a conventional resistance furnace. When placed in the furnace, the upper end of the tube 12 projects above the furnace 14 far enough so as to be unheated. A header member 16 is secured by o-ring seals 18 to the top open end of the tube 12. A source of inert argon gas 20 flows through a valve 22 to the interior of the header 16 and the tube 12 when the valve 22 is opened. The tube and the header are vented through a valve 24. The valve 24 is connected to a manostat 26 which can be adjusted to set the pressure inside the interior of the header 16 and the tube 12.
A middle chalcogen in accordance with this invention comprises the elements sulfur, selenium and tellurium. It is to be noted that oxygen and polonium which often are classified as chalcogens are not considered within the group of elements of middle chalcogens.
A solid phase elemental middle chalcogen is placed in the bottom of tube 12 which is then lowered into the furnace 14 and heated such that this material vaporizes completely. The vaporized chalcogen then condenses as a liquid on the wall of the tube 12 close to its upper closed end. The condensed liquid runs down the side of the tube into the furnace, boiling again when it reaches the temperature which its vapor pressure is equal to the ambient pressure, i.e., that pressure established by the manostat 26. By this refluxing action the inert argon gas is displaced out through the manostat until finally a vaporized chalcogen is established in the interior of the tube 12 at a controlled pressure.
The header 16 is provided with a horizontal portion 30 which receives metal pellets. A pusher mechanism 32 when moved horizontally causes these metal pellets to drop down the center line of the header 16 into the tube 12 without touching the walls of the header or the tube. It should be noted at this point that pellets of metal alloys are also useful if mixed compounds of chalcogenides are desired.
The metal pellets react with the vaporized chalcogen. Once started, the reaction continues spontaneously during free fall of the pellets as the result of the rapid release of heat of reaction. The tube 12 is selected to be long enough so that the reaction is completed before the metal pellets reach the lower end of the tube. As a result of this reaction, metal chalcogenides are produced in the form of a fine powder which deposits on the wall of the tube. The rate of reaction is controlled by controlling the pressure, the rate of addition of metal, and the temperature of the furnace 14. Elemental sulfur, selenium and tellurium can be obtained commercially in extremely pure states. Moreover, argon which is extremely pure is also commercially available. Further, the high temperature reaction occurs away from the walls of the tube 12 during free fall. As a consequence of the above, the resulting chalcogenides are not contaminated with metal oxides.
For example, in order to prepare copper sulfide, the temperature of the furnace 14 was maintained at 1150° C. and the pressure at one atmosphere. Copper pellets of 1 mm diameter were dropped into the sulfur vapor and burned rapidly to produce copper sulfide (CuS). In preparing silver selenide (AgSe), a furnace temperature of 1100° C. and atmospheric pressure were found effective. By using a tube 12 of 5 cm diameter and 1 meter in length, approximately 2 moles of these compounds were prepared in single batches. The compounds were not contaminated with metal oxides.
The invention has been described in detail with particular reference to a certain preferred embodiment thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims (2)

I claim:
1. A method of preparing a metal chalcogenide, comprising the steps of:
(a) placing a solid phase elemental middle chalcogen into a container;
(b) providing an inert gas atmosphere in such container;
(c) heating such container to vaporize the solid phase elemental chalcogen and displace the inert gas previously provided in the container; and
(d) dropping pellets consisting of an elemental metal into such container without touching its walls such that the metal pellets react with the vaporized chalcogen to form a metal chalcogenide.
2. The method of claim 1 wherein the metal is selected from the group consisting of cadmium, zinc, silver, copper, indium or tin and alloys thereof.
US06/877,084 1986-06-23 1986-06-23 Method of synthesis of inorganic chalcogenides Expired - Fee Related US4676969A (en)

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US06/877,084 US4676969A (en) 1986-06-23 1986-06-23 Method of synthesis of inorganic chalcogenides

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2628120A1 (en) * 1988-03-07 1989-09-08 Vachey Lucien PROCESS FOR THE MANUFACTURE OF A MASS BLACKED SILVER ALLOY
US20040089410A1 (en) * 1999-05-02 2004-05-13 Yeda Research & Development Co., Ltd. Bulk synthesis of long nanotubes of transition metal chalcogenides
CN103373714A (en) * 2012-04-24 2013-10-30 长沙联恒科技有限公司 Production method of tungsten selenide and production equipment thereof
EP2689840A1 (en) * 2012-07-25 2014-01-29 Karl Rimmer Method and device for producing metal chalcogenides
EP3845303A1 (en) * 2019-12-30 2021-07-07 Karl Rimmer Method for the preparation of antimony trisulfide

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2358661A (en) * 1942-12-26 1944-09-19 Dow Chemical Co Production of magnesium sulphide
GB630042A (en) * 1946-07-09 1949-10-04 Int Hydrogeneeringsoctrooien Process of sulphiding solids
US3691088A (en) * 1970-10-30 1972-09-12 Sylvania Electric Prod Process for preparing phosphors
US3773909A (en) * 1971-09-20 1973-11-20 Eastman Kodak Co Chalcogenide spinel powders
US4007055A (en) * 1975-05-09 1977-02-08 Exxon Research And Engineering Company Preparation of stoichiometric titanium disulfide
US4348299A (en) * 1980-08-27 1982-09-07 Rca Corporation Method for preparing inorganic sulfides

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2358661A (en) * 1942-12-26 1944-09-19 Dow Chemical Co Production of magnesium sulphide
GB630042A (en) * 1946-07-09 1949-10-04 Int Hydrogeneeringsoctrooien Process of sulphiding solids
US3691088A (en) * 1970-10-30 1972-09-12 Sylvania Electric Prod Process for preparing phosphors
US3773909A (en) * 1971-09-20 1973-11-20 Eastman Kodak Co Chalcogenide spinel powders
US4007055A (en) * 1975-05-09 1977-02-08 Exxon Research And Engineering Company Preparation of stoichiometric titanium disulfide
US4348299A (en) * 1980-08-27 1982-09-07 Rca Corporation Method for preparing inorganic sulfides

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Ulrich, G., A Guide to Chemical Engineering Process Design and Economics, Wiley & Sons, pp. 136 137, 1984. *
Ulrich, G., A Guide to Chemical Engineering Process Design and Economics, Wiley & Sons, pp. 136-137, 1984.

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2628120A1 (en) * 1988-03-07 1989-09-08 Vachey Lucien PROCESS FOR THE MANUFACTURE OF A MASS BLACKED SILVER ALLOY
WO1989008612A1 (en) * 1988-03-07 1989-09-21 Lucien Vachey Process for manufacturing integrally-blackened silver alloy
US5067987A (en) * 1988-03-07 1991-11-26 Lucien Vachey Method of manufacturing a silver alloy which is blackened throughout its bulk
US20040089410A1 (en) * 1999-05-02 2004-05-13 Yeda Research & Development Co., Ltd. Bulk synthesis of long nanotubes of transition metal chalcogenides
US6841142B1 (en) * 1999-05-02 2005-01-11 Yeda Research And Development Co., Ltd. Bulk synthesis of long nanotubes of transition metal chalcogenides
US20060071165A1 (en) * 1999-05-02 2006-04-06 Yeda Research & Development Co., Ltd. Bulk synthesis of long nanotubes of transition metal chalcogenides
CN103373714A (en) * 2012-04-24 2013-10-30 长沙联恒科技有限公司 Production method of tungsten selenide and production equipment thereof
EP2689840A1 (en) * 2012-07-25 2014-01-29 Karl Rimmer Method and device for producing metal chalcogenides
AT513164A1 (en) * 2012-07-25 2014-02-15 Rimmer Karl Dipl Ing Dr Process and apparatus for the production of metal chalcogenides
AT513164B1 (en) * 2012-07-25 2015-06-15 Rimmer Karl Dipl Ing Dr Process and apparatus for the production of metal chalcogenides
EP3845303A1 (en) * 2019-12-30 2021-07-07 Karl Rimmer Method for the preparation of antimony trisulfide

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